Polymerization catalyst compositions and processes to produce polymers and bimodal polymers

ABSTRACT

A process to produce a first catalyst composition is provided. The process comprises contacting at least one first organometal compound and at least one activator to produce the first catalyst composition. The activator is selected from the group consisting of aluminoxanes, fluoro-organo borates, and treated solid oxide components in combination with at least one organoaluminum compound. In another embodiment of this invention, a process to produce a second catalyst composition for producing bimodal polymers is provided. The process comprises contacting at least one first organometal compound, at least one activator, and at least one second organometal compound to produce the second catalyst composition. The first and second catalyst compositions are also provided as well as polymerization processes using these compositions to produce polymers.

FIELD OF THE INVENTION

[0001] This invention is related to the field of polymerization catalystcompositions.

BACKGROUND OF THE INVENTION

[0002] Zirconium based metallocene polymerization catalysts, such as,bis(cyclopentadienyl)zirconium dichloride, are well known and arecommonly used as ethylene polymerization catalysts when combined withactivators, such as, for example, methylaluminoxane (MAO). A descriptionof such catalysts can be found, for example, in Angew. Chem. 88, 689,1976, Justus Liebigs Ann. Chem. 1975, 463, and U.S. Pat. No. 5,324,800,herein incorporated by reference. Zirconium based metallocenes can bequite active, but unfortunately, these metallocenes also produce afairly narrow molecular weight distribution.

[0003] For many extrusion grade applications, such as film, pipe, andblow molding, polymers having broad molecular weight distributions arepreferred. Especially preferred are so-called “bimodal distribution”polymers because of the superior toughness imparted to the finalmanufactured resin part. See, for example, U.S. Pat. Nos. 5,306,775 andU.S. Pat. No. 5,319,029, herein incorporated by reference. The superiortoughness can result from concentrating the short chain branching in thehigh molecular weight portion of the molecular weight distribution.Extremely long and highly branched chains can be more effective as tiemolecules between the crystalline phases. These tie molecules can imparthigher impact resistance and environmental stress crack resistance tobimodal polymers.

[0004] To produce such bimodal polymers from metallocene catalysts, itis necessary to combine two metallocenes. A first metallocene isutilized to produce a low molecular weight polymer having littlebranching. Zirconium based metallocenes can function well in such arole. A second metallocene is utilized to produce the high molecularweight polymer, and this second metallocene should also simultaneouslyincorporate comonomers, such as hexene, very well. In this way, thelongest chains contain the most branching, which is ideal for theproduction of bimodal polymers.

[0005] Unfortunately, the requirements of the second metallocene hasbeen difficult to fill. Of the zirconium based metallocenes describedpreviously, few generate very high molecular weight polymer. Of thesefew, activity or stability is often poor, and comonomer incorporation isnot impressive. A second class of metallocene catalysts, calledhalf-sandwich titanium based metallocenes, do produce very highmolecular weight polymer, and some even incorporate hexene well. SeeOrganometallics, 1966, 15, 693-703 and Macromolecules 1998, 31,7588-7597. Half-sandwich titanium based metallocenes have a titaniumbonded to one cyclopentadienyl, indenyl, or fluorenyl group. However,these compounds are not noted for their high activity.

[0006] There is a need in the polymer industry for a metallocenecatalyst or organometal catalyst that produces high molecular weightpolymer, has a high activity, and incorporates comonomers efficientlythat can be used alone or in combination with other metallocenes.

[0007] It is an object of this invention to provide a first organometalcompound capable of producing high molecular weight polymers.

[0008] It is another object of this invention to provide a process forproducing a first catalyst composition. The process comprises contactingat least one first organometal compound and at least one activator.

[0009] It is another object of this invention to provide the firstcatalyst composition.

[0010] It is another object of this invention to provide apolymerization process. The process comprises contacting the firstcatalyst composition with one or more alpha olefins in a polymerizationzone under polymerization conditions to produce a high molecular weightpolymer.

[0011] It is another object of this invention to provide the highmolecular weight polymer.

[0012] It is another object of this invention to provide a process forproducing a second catalyst composition capable of producing bimodalpolymers. The process comprises contacting the first organometalcompound, at least one activator, and at least one second organometalcompound.

[0013] It is another object of this invention to provide the secondcatalyst composition capable of producing bimodal polymers.

[0014] It is a further object of this invention to provide a process forthe production of bimodal polymers. The process comprises contacting thesecond catalyst composition with one or more alpha olefins in apolymerization zone under polymerization conditions to produce thebimodal polymers.

[0015] It is yet a further object of this invention to provide thebimodal polymer.

SUMMARY OF THE INVENTION

[0016] According to one embodiment of this invention, a process toproduce a first catalyst composition is provided. The process comprisescontacting at least one first organometal compound and at least oneactivator to produce the first catalyst composition;

[0017] wherein the first organometal compound is represented by theformula

R₂CpM¹—O—M²CpR₂

[0018] wherein M¹ is selected from the group consisting of titanium,zirconium, and hafnium;

[0019] wherein M² is selected from the group consisting of a transitionmetal, a lanthamide metal, an actinide metal, a Group IIIB metal, aGroup IVB metal, a Group VB metal, and a Group VIB metal;

[0020] wherein Cp is independently selected from the group consisting ofcyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls,substituted indenyls, and substituted fluorenyls;

[0021] wherein substituents on the substituted cyclopentadienyls,substituted indenyls, and substituted fluorenyls of Cp are selected fromthe group consisting of aliphatic groups, cyclic groups, combinations ofaliphatic and cyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, silicon,phosphorus, boron, germanium, and hydrogen;

[0022] wherein R is independently selected from the group consisting ofhalides, aliphatic groups, substituted aliphatic groups, cyclic groups,substituted cyclic groups, combinations of aliphatic groups and cyclicgroups, combinations of substituted aliphatic groups and cyclic groups,combinations of aliphatic groups and substituted cyclic groups,combinations of substituted aliphatic groups and substituted cyclicgroups, amido groups, substituted amido groups, phosphido groups,substituted phosphido groups, alkyloxide groups, substituted alkyloxidegroups, aryloxide groups, substituted aryloxide groups, organometallicgroups, and substituted organometallic groups; and

[0023] wherein the activator is selected from the group consisting ofaluminoxanes, fluoro-organo borates, and treated solid oxide componentsin combination with at least one organoaluminum compound.

[0024] In another embodiment of this invention, a process to produce asecond catalyst composition for producing bimodal polymers is provided.The process comprises contacting at least one first organometalcompound, at least one activator, and at least one second organometalcompound to produce the second catalyst composition;

[0025] wherein the second organometal compound is represented by theformula, (C₅R₅)₂ZrX₂;

[0026] wherein the R is the same or different and is independentlyselected from the group consisting of hydrogen and a hydrocarbyl grouphaving from 1 to about 10 carbon atoms;

[0027] wherein the hydrocarbyl group is selected from the groupconsisting of a linear or branched alkyl, a substituted or unsubstitutedaryl, and an alkylaryl; and

[0028] wherein X is the same or different and is independently selectedfrom the group consisting of a halide, an alkyl, an alkylaryl havingfrom 1 to about 10 carbon atoms, and a triflate.

BRIEF DESCRIPTION OF DRAWING

[0029]FIG. 1 is a graph showing the polymer molecular weightdistribution (MWD). The normalized weight fraction per increment of logM [dW/d(log M)] is plotted as a function of the molecular weight (M) ingrams per mole (g/mol), plotted on a logarithmic (log) scale.

DETAILED DESCRIPTION OF THE INVENTION

[0030] In a first embodiment of this invention, a process to produce afirst catalyst composition is provided. The process comprises contactingat least one first organometal compound and at least one activator. Thefirst organometal compound is represented by the formula:

R₂CpM¹—O—M²CpR₂

[0031] In this formula, M¹ is selected from the group consisting oftitanium, zirconium, and hafnium. Currently, it is preferred when M¹ istitanium. M² is selected from the group consisting of a transitionmetal, a lanthamide, an actinide, a Group IIIB metal, a Group IVB metal,a Group VB metal, and a Group VIB metal. Preferably, M² is titanium.

[0032] In this formula, Cp is independently selected from the groupconsisting of cyclopentadienyls, indenyls, fluorenyls, substitutedcyclopentadienyls, substituted indenyls, such as, for exampletetrahydroindenyls, and substituted fluorenyls, such as, for example,octahydrofluorenyls.

[0033] Substituents on the substituted cyclopentadienyls, substitutedindenyls, and substituted fluorenyls of Cp are selected from the groupconsisting of aliphatic groups, cyclic groups, combinations of aliphaticand cyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, silicon,phosphorus, boron, germanium, and hydrogen, as long as these groups donot substantially, and adversely, affect the polymerization activity ofthe first organometal compound.

[0034] Suitable examples of aliphatic groups are hydrocarbyls, such as,for example, paraffins and olefins. Suitable examples of cyclic groupsare cycloparaffins, cycloolefins, cycloacetylenes, and arenes.Substituted silyl groups include, but are not limited to, alkylsilylgroups where each alkyl group4 contains from 1 to about 12 carbon atoms,arylsilyl groups, and arylalkylsilyl groups. Suitable alkyl halidegroups have alkyl groups with 1 to about 12 carbon atoms. Suitableorganometallic groups include, but are not limited to, substituted silylderivatives, substituted tin groups, substituted germanium groups, andsubstituted boron groups.

[0035] Suitable examples of such substituents are methyl, ethyl, propyl,butyl, tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl,octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, phenyl,chloro, bromo, iodo, trimethylsilyl, and phenyloctylsilyl.

[0036] In this formula, R is independently selected from the groupconsisting of halides, aliphatic groups, substituted aliphatic groups,cyclic groups, substituted cyclic groups, combinations of aliphaticgroups and cyclic groups, combinations of substituted aliphatic groupsand cyclic groups, combinations of aliphatic groups and substitutedcyclic groups, combinations of substituted aliphatic groups andsubstituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted phosphido groups, alkyloxide groups,substituted alkyloxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, and substituted organometallic groups.

[0037] Preferably, the first organometal compound can be represented bythe following formula:

(C₅R₅)TiX₂—O—(C₅R₅)TiX₂

[0038] In this formula, each R is the same or different and isindependently selected from the group consisting of hydrogen and ahydrocarbyl group having from 1 to about 10 carbon atoms. Thehydrocarbyl group is selected from the group consisting of a linear orbranched alkyl, a substituted or unsubstituted aryl, and an alkylaryl. Xis the same or different and is independently selected from the groupconsisting of a halide, an alkyl, an alkylaryl having from 1 to about 10carbon atoms, and a triflate. Suitable first organometal compoundsinclude, for example, [(C₅H₄CH₃)TiCl₂]₂O, [(C₅H₄CH₂C₆H₅)TiF₂]₂O,[(C₅H₃CH₃C₂H₅)TiBr₂]O, and [(C₅H₅)TiCl₂]₂O. Most preferably, the firstorganometal compound is [(C₅H₅)TiCl₂]₂O. Combinations of these firstorganometal compounds also can be used.

[0039] The activator is selected from the group consisting ofaluminoxanes, fluoro-organo borates, and at least one treated solidoxide component in combination with at least one organoaluminumcompound.

[0040] Aluminoxanes, also referred to as poly(hydrocarbyl aluminumoxides), are well known in the art and are generally prepared byreacting an hydrocarbylaluminum compound with water. Such preparationtechniques are disclosed in U.S. Pat. Nos. 3,242,099 and 4,808,561, theentire disclosures of which are herein incorporated by reference. Thecurrently preferred aluminoxanes are prepared from trimethylaluminum ortriethylaluminum and are sometimes referred to as poly(methyl aluminumoxide) and poly(ethyl aluminum oxide), respectively. It is also withinthe scope of the invention to use an aluminoxane in combination with atrialkylaluminum, such as disclosed in U.S. Pat. No. 4,794,096, thedisclosure of which is herein incorporated by reference.

[0041] Generally, any amount of the aluminoxane capable of activatingthe first organometal compound is utilized in this invention.Preferably, the molar ratio of the aluminum in the aluminoxane to thetransition metal in the metallocene is in a range of about 1:1 to about100,000:1, and, most preferably, 5:1 to 15,000:1. Generally, the amountof aluminoxane added to a polymerization zone is an amount within arange of about 0.01 mg/L to about 1000 mg/L, preferably about 0.1 mg/Lto about 100 mg/L. Most preferably, the amount of aluminoxane added isan amount within a range of 1 to 50 mg/L in order to maximize catalystproductivity and activity.

[0042] Fluoro-organo borate compounds also can be used to activate andform the first catalyst composition. Any fluoro-organo borate compoundknown in the art that is capable of activating an organometal compoundcan be utilized. Examples of such fluoro-organo borate compoundsinclude, but are not limited to, fluorinated aryl borates, such as,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)boron,N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, andmixtures thereof. Although not intending to be bound by theory, theseexamples of fluoro-organo borate compounds and related fluoro-organoborates are thought to form “weakly-coordinating” anions when combinedwith organometal compounds as disclosed in U.S. Pat. No. 5,919,983,herein incorporated by reference.

[0043] Generally, any amount of fluoro-organo borate compound capable ofactivating the organometal compound is utilized in this invention.Preferably, the amount of the fluoro-organo borate compound is in arange of from about 0.5 mole to about 10 moles of fluoro-organo boratecompound per mole of organometal compound. Most preferably, the amountof the fluoro-organo borate compound is in a range of from 0.8 mole to 5moles of fluoro-organo borate compound per mole of organometal compound.

[0044] The aluminoxane and fluoro-organo borate compounds can besupported or unsupported. If supported, generally the support is aninorganic oxide, such as, silica, an aluminate, or combinations thereof.The use of a supported activator can result in a heterogeneous catalystcomposition, and an unsupported activator can result in a homogeneouscatalyst composition.

[0045] Preferably, the activator is a treated solid oxide component usedin combination with an organoaluminum compound. The treated solid oxidecomponent is a halided solid oxide component or a halided,metal-containing solid oxide component. The halided solid oxidecomponent comprises a halogen and a solid oxide component. The halided,metal-containing solid oxide component comprises a halogen, a metal, anda solid oxide component.

[0046] The organoaluminum compound can be represented by the followingformula:

AlR_(3-n)X_(n)

[0047] In this formula, R is the same or different and is selected fromthe group consisting of hydride and a hydrocarbyl group having 1 toabout 10 carbon atoms. The hydrocarbyl group is selected from the groupconsisting of a linear or branched alkyl, a substituted or unsubstitutedaryl and an alkylaryl. X is selected from the group consisting ofhalides and hydrocarbyloxides. The hydrocarbyloxide is selected from thegroup consisting of a linear or branched alkoxide, a substituted orunsubstituted aryloxide and an alkylaryloxide. The number n is either 1or 0. Suitable organoaluminum compounds include, for example,triisobutylaluminum, diethylaluminum hydride, dipentylalumium ethoxide,dipropylaluminum phenoxide, and the mixtures thereof. Preferably, theorganoaluminum compound is trialkylaluminum. Most preferably, it istriisobutylaluminum or triethylaluminum. Combinations of theseorganoaluminum compounds also can be used.

[0048] The solid oxide component is prepared from an aluminate selectedfrom the group consisting of alumina, silica-alumina, aluminophosphate,aluminoborate, and mixtures thereof. Preferably, the solid oxidecomponent is alumina. The halogen is selected from the group consistingof chlorine and bromine. Preferably, for highest activity, the halogenis chlorine. The metal is selected from the group consisting of zinc,nickel, vanadium, silver, copper, gallium, tin, tungsten, andmolybdenum. Preferably, for high activity and low cost, the metal iszinc.

[0049] The solid oxide component has a pore volume greater than about0.5 cc/g, preferably, greater than about 0.8 cc/g, and most preferably,greater than 1.0 cc/g. The solid oxide component has a surface area in arange of about 100 to about 1000 m²/g, preferably from about 200 toabout 800 m²/g, and most preferably, from 250 to 600 m²/g.

[0050] To produce the halided solid oxide component, the solid oxidecomponent is calcined either prior to, during, or after contacting witha halogen-containing compound. Generally, calcining is conducted forabout 1 minute to about 100 hours, preferably for about 1 hour to about50 hours, and most preferably, from 3 hours to 20 hours. The calciningis conducted at a temperature in a range of about 200 to about 900° C.,preferably, in a range of about 300 to about 800° C. , and mostpreferably, in a range of 400 to 700° C. Any type of suitable ambientcan be used during calcining. Generally, calcining can be completed inan inert atmosphere. Alternatively, an oxidizing atmosphere, such as,for example, oxygen or air, or a reducing atmosphere, such as, forexample, hydrogen or carbon monoxide, can be used.

[0051] The halogen-containing compound is at least one compound selectedfrom the group consisting of chlorine-containing compounds andbromine-containing compounds. The halogen-containing compound can be ina liquid or preferably, a vapor phase. The solid oxide component can becontacted with the halogen-containing compound by any means known in theart. Preferably, the halogen-containing compound can be vaporized into agas stream used to fluidize the solid oxide component during calcining.The solid oxide component is contacted with the halogen-containingcompound generally from about 1 minute to about 10 hours, preferably,from about 5 minutes to about 2 hours, and most preferably, from 10minutes to 30 minutes. Generally, the solid oxide component is incontact with the halogen-containing compound at a temperature in therange of about 200 to about 900° C., preferably, at a temperature in arange of about 300 to about 800° C., and most preferably, in a range of400 to 700° C. Any type of suitable ambient can be used to contact thesolid oxide component and the halogen-containing compound. Preferably,an inert atmosphere is used. Alternatively, an oxidizing or reducingatmosphere can also be used.

[0052] Suitable halogen-containing compounds include volatile or liquidorganic chloride or bromide compounds and inorganic chloride or bromidecompounds. Organic chloride or bromide compounds can be selected fromthe group consisting of carbon tetrachloride, chloroform,dichloroethane, hexachlorobenzene, trichloroacetic acid, bromoform,dibromomethane, perbromopropane, and mixtures thereof. Inorganicchloride or bromide compounds can be selected from the group consistingof gaseous hydrogen chloride, silicon tetrachloride, tin tetrachloride,titanium tetrachloride, aluminum trichloride, boron trichloride, thionylchloride, sulfuryl chloride, hydrogen bromide, boron tribromide, silicontetrabromide, and mixtures thereof. Additionally, chlorine and brominegas can be used. Optionally, a fluorine-containing compound or fluorinegas can also be included when contacting the solid oxide component withthe halogen-containing compound to achieve higher activity in somecases.

[0053] The amount of halogen present in the halided solid oxidecomponent is generally in the range of about 2 to about 150% by weight,preferably about 10% to about 100% by weight, and most preferably, 15%to 75% by weight, where the weight percents are based on the weight ofthe halided solid oxide component before calcining or the amount addedto a precalcined solid oxide component.

[0054] To produce the halided, metal-containing solid oxide component,the solid oxide component first is treated with a metal-containingcompound The metal-containing compound can be added to the solid oxidecomponent by any method known in the art. In a first method, the metalcan be added to the solid oxide component by cogellation of aqueousmaterials, as disclosed in U.S. Pat. Nos. 3,887,494; 3,119,569;4,405,501; 4,436,882; 4,436,883; 4,392,990; 4,081,407; 4,981,831; and4,152,503; the entire disclosures of which are hereby incorporated byreference.

[0055] In a second method, the metal-containing compound can be added tothe solid oxide component by cogellation in an organic or anhydroussolution as disclosed in U.S. Pat. Nos. 4,301,034; 4,547,557; and4,339,559; the entire disclosures of which are hereby incorporated byreference.

[0056] The preferred method is to impregnate the solid oxide componentwith an aqueous or organic solution of a metal-containing compound priorto calcining to produce a metal-containing solid oxide component. Asuitable amount of the solution is utilized to provide the desiredconcentration of metal after drying. The metal-containing solid oxidecomponent then is dried by any suitable method known in the art. Forexample, the drying can be accomplished by vacuum drying, spray drying,or flash drying.

[0057] Any metal-containing compound known in the art that canimpregnate the solid oxide component with the desired metal can be usedin this invention. The metal-containing compound can be any watersoluble salt, such as, for example, nickel nitrate, zinc chloride,copper sulfate, silver acetate, or vanadyl sulfate. The metal-containingcompound can also be an organometallic compound, such as, for example,nickel acetylacetonate, vanadium ethylhexanoate, zinc naphthenate, andmixtures thereof.

[0058] Generally, the amount of metal present is in the range of about0.1 to about 10 millimoles per gram of solid oxide component beforecalcining. Preferably, the amount of metal present is in the range ofabout 0.5 to about 5 millimoles per gram of solid oxide component beforecalcining. Most preferably, the amount of metal present is in the rangeof 1 to 3 millimoles per gram of solid oxide component before calcining.

[0059] After the solid oxide component is combined with themetal-containing compound to produce a metal-containing solid oxidecomponent, it then is calcined for about 1 minute to about 100 hours,preferably for about 1 hour to about 50 hours, and most preferably, from3 hours to 20 hours. The calcining is conducted at a temperature in arange of about 200 to about 900° C., preferably, in a range of about 300to about 800° C. , and most preferably, in a range of 400 to 700° C. Anytype of suitable ambient can be used during calcining. Generally,calcining can be completed in an inert atmosphere. Alternatively, anoxidizing atmosphere, such as, for example, oxygen or air, or a reducingatmosphere, such as, for example, hydrogen or carbon monoxide, can beused.

[0060] After or during calcining, the metal-containing solid oxidecomponent is contacted with a halogen-containing compound to produce thehalided, metal-containing solid oxide component. Methods for contactingthe metal-containing solid oxide component with the halogen-containingcompound are the same as discussed previously for the halided solidoxide component.

[0061] Optionally, the metal containing solid oxide component also canbe treated with a fluorine-containing compound before, during, or aftercontacting the halogen-containing compound, which can further increasethe activity. Any fluorine-containing compound capable of contacting thesolid oxide component during the calcining step can be used. Organicfluorine-containing compounds of high volatility are especially useful.Such organic fluorine-containing compounds can be selected from thegroup consisting of freons, perfluorohexane, perfluorobenzene,fluoromethane, trifluoroethanol, and mixtures thereof. Gaseous hydrogenfluoride or fluorine itself can be used. One convenient method ofcontacting the solid oxide component is to vaporize afluorine-containing compound into a gas stream used to fluidize thesolid oxide component during calcination.

[0062] In a preferred first embodiment, a process to produce a firstcatalyst composition is provided. The process comprises contacting,bis(cyclopentadienyl titanium dichloride)oxide, (CpTiCl₂)₂O, achlorided, zinc-containing alumina, and an organoaluminum compoundselected from the group consisting of triisobutyl aluminum andtriethylaluminum to produce the first catalyst composition. The amountof zinc present is in the range of about 0.5 millimoles to about 5millimoles of zinc per gram of alumina. The chloriding treatmentconsists of exposure to a volatile chlorine-containing compound at about500 to about 700° C.

[0063] The catalyst compositions of this invention can be produced bycontacting the first organometal compound and the activator together.This contacting can occur in a variety of ways, such as, for example,blending. Furthermore, each of these compounds can be fed into thereactor separately, or various combinations of these compounds can becontacted together before being further contacted in the reactor, or allthree compounds can be contacted together before being introduced intothe reactor.

[0064] Currently, one method is to first contact a first organometalcompound and the treated solid oxide component together, for about 1minute to about 24 hours, preferably, about 1 minute to about 1 hour, ata temperature from about 10° C. to about 100° C., preferably 15° C. to50° C., to form a first mixture, and then contact this first mixturewith an organoaluminum compound to form the first catalyst composition.

[0065] Another method is to precontact the first organometal compound,the organoaluminum compound, and the treated solid oxide componentbefore injection into a polymerization reactor for about 1 minute toabout 24 hours, preferably, 1 minute to 1 hour, at a temperature fromabout 10° C. to about 200° C., preferably 20° C. to 80° C. to producethe first catalyst composition.

[0066] A weight ratio of the organoaluminum compound to the treatedsolid oxide component in the first catalyst composition ranges fromabout 5:1 to about 1:1000, preferably, from about 3:1 to about 1:100,and most preferably, from 1:1 to 1:50.

[0067] A weight ratio of the treated solid oxide component to the firstorganometal compound in the first catalyst composition ranges from about10,000:1 to about 1:1, preferably, from about 1000:1 to about 10:1, andmost preferably, from 250:1 to 20:1. These ratios are based on theamount of the components combined to give the first catalystcomposition.

[0068] When the treated solid oxide component is utilized, aftercontacting the compounds, the first catalyst composition comprises apost-contacted first organometal compound, a post-contactedorganoaluminum compound, and a post-contacted treated solid oxidecomponent. It should be noted that the post-contacted solid oxidecomponent is the majority, by weight, of the first catalyst composition.Often times, specific components of a catalyst are not known, therefore,for this invention, the first catalyst composition is described ascomprising post-contacted compounds.

[0069] A weight ratio of the post-contacted organoaluminum compound tothe post-contacted treated solid oxide component in the first catalystcomposition ranges from about 5:1 to about 1:1000, preferably, fromabout 3:1 to about 1:100, and most preferably, from 1:1 to 1:50.

[0070] A weight ratio of the post-contacted treated solid oxidecomponent to the post-contacted first organometal compound in the firstcatalyst composition ranges from about 10,000:1 to about 1:1,preferably, from about 1000:1 to about 10:1, and most preferably, from250:1 to 20:1.

[0071] When comparing activities, the polymerization runs should occurat the same polymerization conditions. It is preferred if the activityof the first catalyst composition is greater than about 1000 grams ofpolymer per gram of activator per hour, more preferably greater thanabout 2000, and most preferably greater than 3000. This activity ismeasured under slurry polymerization conditions, using isobutane as thediluent, and with a polymerization temperature of 90° C., and anethylene pressure of 550 psig. The reactor should have substantially noindication of any wall scale, coating or other forms of fouling.

[0072] One of the important aspects of this invention is that noaluminoxane needs to be used in order to form the first catalystcomposition. Aluminoxane is an expensive compound that greatly increasespolymer production costs. This also means that no water is needed tohelp form such aluminoxanes. This is beneficial because water cansometimes kill a polymerization process. It should be noted that nofluorophenyl borate or other fluoro-organo boron compounds need to beused in order to form the first catalyst composition. Additionally, noorganochromium compounds or MgCl₂ need to be added to form theinvention. Although aluminoxane, fluoro-organo boron compounds,organochromium compounds, or MgCl₂ are not needed in the preferredembodiments, these compounds can be used in other embodiments of thisinvention.

[0073] In a second embodiment of this invention, a process comprisingcontacting at least one monomer and the first catalyst composition toproduce at least one polymer is provided. The term “polymer” as used inthis disclosure includes homopolymers and copolymers. The first catalystcomposition can be used to polymerize at least one monomer to produce ahomopolymer or a copolymer. Usually, homopolymers are comprised ofmonomer residues, having 2 to about 20 carbon atoms per molecule,preferably 2 to about 10 carbon atoms per molecule. Currently, it ispreferred when at least one monomer is selected from the groupconsisting of ethylene, propylene, 1-butene, 3-methyl-1-butene,1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and mixturesthereof.

[0074] When a homopolymer is desired, it is most preferred to polymerizeethylene or propylene. When a copolymer is desired, the copolymercomprises monomer residues and one or more comonomer residues, eachhaving from about 2 to about 20 carbon atoms per molecule. Suitablecomonomers include, but are not limited to, aliphatic 1-olefins havingfrom 3 to 20 carbon atoms per molecule, such as, for example, propylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and otherolefins and conjugated or nonconjugated diolefins such as 1,3-butadiene,isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 1,4-pentadiene,1,7-hexadiene, and other such diolefins and mixtures thereof. When acopolymer is desired, it is preferred to polymerize ethylene and atleast one comonomer selected from the group consisting of 1-butene,1-pentene, 1-hexene, 1-octene, and 1-decene. The amount of comonomerintroduced into a reactor zone to produce a copolymer is generally fromabout 0.01 to about 10 weight percent comonomer based on the totalweight of the monomer and comonomer, preferably, about 0.01 to about 5,and most preferably, 0.1 to 4. Alternatively, an amount sufficient togive the above described concentrations, by weight, in the copolymerproduced can be used.

[0075] Processes that can polymerize at least one monomer to produce apolymer are known in the art, such as, for example, slurrypolymerization, gas phase polymerization, and solution polymerization.It is preferred to perform a slurry polymerization in a loop reactionzone. Suitable diluents used in slurry polymerization are well known inthe art and include hydrocarbons which are liquid under reactionconditions. The term “diluent” as used in this disclosure does notnecessarily mean an inert material; it is possible that a diluent cancontribute to polymerization. Suitable hydrocarbons include, but are notlimited to, cyclohexane, isobutane, n-butane, propane, n-pentane,isopentane, neopentane, and n-hexane. Furthermore, it is most preferredto use isobutane as the diluent in a slurry polymerization. Examples ofsuch technology can be found in U.S. Pat. Nos. 4,424,341; 4,501,885;4,613,484; 4,737,280; and 5,597,892; the entire disclosures of which arehereby incorporated by reference.

[0076] The first catalyst composition used in this process produce goodquality polymer particles without substantially fouling the reactor.When the first catalyst composition is to be used in a loop reactor zoneunder slurry polymerization conditions, it is preferred when theparticle size of the treated solid oxide component is in the range ofabout 10 to about 1000 microns, preferably about 25 to about 500microns, and most preferably, 50 to 200 microns, for best control duringpolymerization.

[0077] One novelty of this invention is that butene can be formed duringethylene polymerization. The butene then is copolymerized by theorganometal compound to yield ethylene-butene copolymers even though nobutene is fed to the reactor. Thus, the polymers produced from theinventive catalyst composition can contain up to about 1 weight percentethyl branching even though no butene is fed to the reactor.

[0078] In a third embodiment of this invention, a process is providedwherein the first catalyst composition is further contacted with atleast one second organometal compound to produce a second catalystcomposition capable of producing bimodal polymers. The secondorganometal compound can be represented by the following formula:

(C₅R₅)₂ZrX₂

[0079] In this formula, each R is the same or different and is selectedfrom the group consisting of hydrogen and a hydrocarbyl group havingfrom 1 to about 10 carbon atoms. The hydrocarbyl group is selected fromthe group consisting of a linear or branched alkyl , a substituted orunsubstituted aryl, and an alkylaryl. X is the same or different and isindependently selected from the group consisting of a halide, an alkyl,an alkylaryl having from 1 to about 10 carbon atoms, and a triflate.Suitable organometallic compounds include, for example, (C₅H₄CH₃)₂ZrCl₂,(C₅H₄CH₂C₆H₆)₂ZrF₂, (C₅H₄C₄H₉)₂ZrCl₂, and (C₅H₃CH₃C₂H₅)₂ZrBr₂.Preferably the organometallic compound is (C₅H₄C₄H₉)₂ZrCl₂. Combinationsof these organometal compounds can also be used.

[0080] The type and amount of the activator in the second catalystcomposition is the same as discussed previously for the first catalystcomposition. Generally, the amount of the first organometal compound andthe second organometal compound combined in the second catalystcomposition is the same as the amount of the first organometal in thefirst catalyst composition. The ratio of the first organometal compoundto the second organometal compound ranges from about 1:100 to about100:1.

[0081] The second organometal compound can be contacted with the otheringredients of this catalyst by any method which was suitable for thefirst organometal compound. For example, it can be mixed with the firstorganometal compound in a hydrocarbon solution and pumped into thereactor separately. Or, the second organometal compound can be fed intoa precontacting vessel where all or some of the other ingredients may becontacted before being introduced into the reactor. Alternatively, allof the ingredients can be fed individually into the reactor directly.

[0082] Preferably, the activity of the second catalyst composition issimilar to that for the first catalyst composition. In addition,aluminoxanes, fluoro-organo boron compounds, organochromium compounds,and MgCl₂ are not required to produce the second catalyst composition,therefore providing the same benefits as previously discussed for thefirst catalyst composition.

[0083] The second catalyst composition can be used in the polymerizationprocesses as discussed previously for the first catalyst composition.When making bimodal polymers according to this third embodiment, it ispreferred to add comonomer and hydrogen in the polymerization reactionzone. Hydrogen can be used to control molecular weight, and comonomercan be used to control polymer density.

EXAMPLES

[0084] Preparation of (CpTiCl₂)₂O:

[0085] Under a dry nitrogen atmosphere, 600 mL of dry tetrahydrofuran(THF) were added to a flask containing 64.70 grams of cyclopentadienyltitanium trichloride obtained from the Strem Company to produce amixture. The mixture formed a first solution as the orange soliddissolved in the THF. Then, a second solution containing 200 mL of THFand 5.309 grams of water was added dropwise over a period of about 15minutes while the first solution was stirred vigorously to produce athird solution. The color of the third solution turned slightly morereddish. The third solution then was heated gently to 40° C. and allowedto stand at that temperature for several hours. After standing at roomtemperature for an additional 24 hours, the THF then was evaporatedunder vacuum leaving a yellow-brown solid of (CpTiCl₂)₂O.

[0086] Preparation of the Chlorided, Zinc-Containing Alumina:

[0087] A commercial alumina sold as Ketjen grade B alumina was obtainedfrom Akzo Nobel Chemical having a pore volume of about 1.78 cc/g and asurface area of about 350 m²/g. A solution of 435 mls of deionizedwater, 34.65 grams of zinc chloride, and 2.5 mls of nitric acid was madeand impregnated onto a 170.35 gram sample of Ketjen Grade B alumina toproduce a zinc-containing alumina. Thus, the zinc chloride loading was20% by weight of the alumina. The zinc-containing alumina then was driedovernight under vacuum at 100° C. and pushed through an 80 mesh screen.A portion of the zinc-containing alumina then was calcined in dry air at600° C. for three hours to convert the zinc species to a mixed zincoxide producing a calcined, zinc-containing alumina. Then, the calcined,zinc-containing alumina was activated in 25 gram batches as follows. 25grams of the calcined, zinc-containing alumina was heated under nitrogento 600° C. again and while still at 600° C., 2.4 mls of carbontetrachloride were injected into the gas stream where it evaporated andwas carried up through the fluidizing zinc-containing alumina bed toproduce a chlorided, zinc-containing alumina. The chlorided,zinc-containing alumina then was stored under dry nitrogen and latertested for polymerization activity.

[0088] Bench Scale Polymerization Runs:

[0089] Bench scale polymerizations runs were carried out in a one gallonstirred Autoclave Engineers reactor. It was first prepared for use bypurging with nitrogen and heating the empty reactor to 120° C. Aftercooling to below 40° C. and purging with isobutane vapors, a smallamount of the organometal compound, usually from 0.001 to 0.01 grams asindicated, was charged to the reactor under nitrogen. Then, anactivator, such as a MAO solution, was added, and the reactor wasclosed. Next, 1-hexene, if used, was injected into the reactor, followedby two liters of isobutane liquid added under pressure to produce areaction mixture. The reactor was subsequently heated to the desiredtemperature, usually 90° C., or as otherwise indicated. The reactionmixture was stirred at 700 revolutions per minute (rpm). In some runs,while heating, hydrogen was added to the reactor from one of twoauxiliary vessels of 55 cc (SV) or 325 cc (LV) volume. The amount ofhydrogen added was measured and expressed by the pressure drop on thisvessel as its contents were added the reactor. The final partialpressure of hydrogen on the reactor itself can be determinedapproximately by multiplying the measured pressure drop from theseauxiliary vessels by 0.163 (LV) or by 0.028 (SV). Ethylene then wasadded to the reactor and fed on demand to maintain a fixed totalpressure of 450 psig, or as otherwise indicated. The reactor wasmaintained at the specified temperature for about 60 minutes. Then, theisobutane and ethylene were vented from the reactor, and the reactorthen was opened. The polymer was collected usually as a dry powder. Insome cases, the polymer stuck to the reactor walls and had to be scrapedoff for recovery.

[0090] When a halided, metal-containing solid oxide component was usedas the activator, typically 0.25 grams of the halided, metal-containingsolid oxide component was sealed in a glass tube to which a toluenesolution containing from 2 to 20 mg of the organometal compound wereadded as well as 1 mL of a 1 molar heptane solution of theorganoaluminum, usually triethylaluminum, to produce a pre-contactedcatalyst mixture. The pre-contacted catalyst mixture then was added tothe reactor under nitrogen.

[0091] Ethylene was polymerization grade ethylene obtained from UnionCarbide Corporation. The ethylene was purified further through a columnof ¼ inch beads of Alcoa A201 alumina that had been activated at 250° C.in nitrogen. Isobutane was polymerization grade obtained from PhillipsPetroleum Co., Borger, Tex. It was purified further by distillation, andit too was passed through a column of ¼ inch beads of Alcoa A201 aluminathat had been activated at 250° C. in nitrogen. The 1-hexene waspolymerization grade obtained from Chevron Chemicals. It was purifiedfurther by nitrogen purging and storage over 13× molecular sieves thathad been activated at 250° C. The methylaluminoxane (MAO) was obtainedfrom Albemarle Corporation as a 10% solution in toluene. Otherorganoaluminum compounds were obtained from Akzo Corporation as onemolar solutions in heptane.

[0092] Polymer Tests:

[0093] Bulk density was determined in lbs/ft as described in ASTMD1895-89, by weighing a 100 ml graduated cylinder in which polymer fluffhad been lightly tapped.

[0094] Polymer density was determined in grams per cubic centimeter(g/cc) on a compression molded sample, cooled at about 15° C. per hourand conditioned for about 40 hours at room temperature in accordancewith ASTM D1505-68 and ASTM D1928, procedure C.

[0095] Melt Index (MI) in grams of polymer per ten minutes wasdetermined in accordance with ASTM D1238, condition 190/2, at 190° C.with a 2,160 gram weight. 190° C.

[0096] High load melt index (HLMI, g/10 min) was determined inaccordance with ASTM D1238, Condition 190/2.16, at 190° C. with a 21,600gram weight.

[0097] Molecular weights and molecular weight distributions wereobtained using a Waters 150 CV gel permeation chromatograph (GPC) withtrichlorobenzene (TCB) as the solvent, with a flow rate of 1 mL/minuteat a temperature of 140° C. BHT (2,6-di-tert-butyl-4-methylphenol) at aconcentration of 1.0 g/L was used as a stabilizer in the TCB. Aninjection volume of 220 microliters were used with a nominal polymerconcentration of 0.3 g/l (at room temperature). Dissolution of thesample in stabilized TCB was carried out by heating at 160-170° C. for20 hours with occasional, gentle agitation. The column was two WatersHT-6E columns (7.8×300 mm). The columns were calibrated with a broadlinear polyethylene standard (Phillips Marlex® polyethylene BHB 5003)for which the molecular weight had been determined.

[0098] Branch analysis was accomplished via solution 13C NMR spectra,which were collected from a deuterated trichlorobenzene solution ofpolymer using either a GEQE200 NMR spectrometer at 75.5 MHZ, or a Varian500 NMR spectrometer at 125.7 MHZ.

Examples 1-28

[0099] A number of bench-scale polymerization runs were made with(CpTiCl₂)₂O and with a number of other related titanium basedorganometal compounds for comparison. The results of these tests arelisted in Table 1.

[0100] In these runs, usually 0.25 g of the chlorided, zinc-containingalumina described previously was charged to the reactor along with a fewmilligrams of the organometal compound, as indicated in the table, and asmall amount of the organoaluminum compound, usually 1 mL or 0.5 mL oftriisobutyl aluminum. In some cases, these ingredients were combined ina glass tube for a short time before being added to the reactor.

[0101] It can be seen from Table 1 that the inventive compound,designated as A in the table, is considerably more active than any othercompound that was tested. Comparative compounds included the closestrelative to the inventive compound, the cyclopentadienyl titaniumdichloride aryloxides, and also the precursor material, cyclopentadienyltitanium trichloride, and even the well-known “constrained geometry”catalyst from Dow. However, none of these compounds approached theactivity exhibited from the inventive compound. Notice also that theinventive compound produced extremely high molecular weight polymer,which is desirable for a bimodal combination of catalysts. TABLE 1Chlorided, Organometal Zinc- Organ- Compound Triiso- Chlorided,Containing ometal Ex- butyl- Zinc- Polymer Alumina Compound ample Temp.Hexene aluminum Containing Yield Time Activity Activity Density # TypeMg deg C. (g) (ml) Alumina (g) (g) (min) (gPE/g/h)* (gPE/g/h)* HLMI(g/cc) 1 A 6.0 80 25 0.5 0.250 339 30 2712 113,000 0.01 0.9289 2 A 6.080 25 0.5 0.250 331 30 2648 110,333 0.11 0.9280 3 A 6.0 80 90 0.5 0.250306 30 2448 102,000 0.06 0.9244 4 B 17.0 80 0 1 0.250 0 22 0 0 5 B 17.080 0 1 0.250 35 51 165 2,422 6 C 18.0 80 0 1 0.250 0 34 0 0 7 C 19.0 800 1 0.250 0 46 0 0 8 D 50.0 90 20 1 0.250 0 38 0 0 9 E 23.0 90 20 10.250 43 60 172 1,870 10 F 7.0 80 0 1 0.150 6 60 40 857 11 F 12.0 70 00.5 0.150 14 60 93 1,167 12 G 10.0 80 25 0.5 0.250 0 30 0 0 13 H 10.0 8025 0.5 0.250 89 30 356 8,900 14 I 10.0 80 25 0.5 0.250 5 30 20 500 15 J4.0 80 25 0.5 0.250 18 30 144 9000 16 J 4.0 80 25 0.5 0.250 20 30 16010,000 17 K 8.0 90 22 1 0.250 121 60 484 15,125 18 K 4.0 80 50 0.5 0.25045 30 360 22,500 0.05 0.9289 19 L 12.0 90 0 1 0.250 0 21 0 0 20 L 5.0 9011 1 0.249 40 30 161 8,000 21 L 10.0 90 20 1 0.250 13 60 52 1,300 22 L4.0 90 41 1 0.258 41 30 159 10,250 23 M 20.5 80 0 1 0.162 38 60 2351,854 24 M 17.4 80 5 1 0.158 33 60 209 1,897 25 M 9.7 80 10 1 0.147 5160 347 5,258 0 0.9309 26 N 6.0 80 25 0.5 0.250 90 30 360 15,000 27 O10.0 80 25 0.5 0.250 0 30 0 0 28 P 10.0 80 25 0.5 0.500 16 60 32 1600

Examples 29-32

[0102] Bench scale polymerization runs were made at 80° C. with theinventive organometal compound A described previously and the chlorided,zinc-containing alumina. In each run, 1 mL of 1 molartriisobutylaluminum was added along with a varying amount of hexene. Thepolymers produced had a HLMI of zero. C-13 NMR branching analysis wasperformed on the polymers, and the following data in Table 2 wereobserved. TABLE 2 Grams Ethyl Butyl Hexene Branches Branches Example No.Added Density (g/cc) Wt % Wt % 29-Inventive 10 0.9319 0.12 1.6230-Inventive 20 0.9300 0.10 3.18 31-Inventive 30 0.9280 0.10 4.6232-Comparative 100 0.9401 0 1.02

[0103] Butyl branching increased, as expected, with increased hexene.The remarkable feature, however, is how much branching is incorporatedwith so little hexene added. This represents a high degree of comonomerincorporation efficiency. NMR detected ethyl branching as well, whichindicates in-situ butene generation. In Comparison Example 32, bis(n-butylcyclopentadienyl) zirconium dichloride, well known for its highactivity and for its ability to produce low molecular weight polymer,incorporated little hexene in comparison to the inventive compound A.

[0104] Thus, the first organometal compound and first catalystcomposition of this invention: 1) displays high activity; 2)incorporates hexene well, and 3) also produces extremely high molecularweight polymer. This is a unique combination of characteristics that isideal for producing bimodal polymers from a combination of organometalcompounds with branching concentrated in the high molecular weight partof the distribution. The comparative compound in Table 2, bis(n-butylcyclopentadienyl) zirconium dichloride, makes an ideal companionto the inventive first catalyst composition because of its highactivity, yet poor incorporation efficiency, and its natural ability toproduce low molecular weight polymer. The two together form an excellentchoice for producing bimodal polymers.

Example 33

[0105] Bimodal Production Runs in Loop Reactor

[0106] Ethylene polymers were prepared also in a continuous particleform process (also known as a slurry process) by contacting a secondcatalyst composition with ethylene and hexene comonomer. The medium andtemperature are thus selected such that the copolymer is produced assolid particles and is recovered in that form. Ethylene that had beendried over activated alumina was used as the monomer. Isobutane that hadbeen degassed by fractionation and dried over alumina was used as thediluent.

[0107] A liquid full 15.2 cm diameter pipe loop reactor having a volumeof 23 gallons (87 liters) was utilized. Liquid isobutane was used as thediluent, and occasionally some hydrogen was added to regulate themolecular weight of the polymer product. The reactor pressure was about4 Mpa (about 580 psi). The reactor temperature was set at 180° F. Thereactor was operated to have a residence time of 1.25 hours. The secondcatalyst composition was added through a 0.35 cc circulating ball-checkfeeder. At steady state conditions, the isobutane feed rate was about 46liters per hour, the ethylene feed rate was about 30 lbs/hr, and the1-hexene feed rate was varied to control the density of the polymerproduct. Ethylene concentration in the diluent was 14 mole percent.Catalyst concentrations in the reactor was such that the second catalystcomposition content ranges from 0.001 to about 1 weight percent based onthe weight of the reactor contents. Polymer was removed from the reactorat the rate of about 25 lbs per hour and recovered in a flash chamber. AVulcan dryer was used to dry the polymer under nitrogen at about 60-80°C.

[0108] The organoaluminum compound, triisobutylaluminum (TIBA), wasobtained from Akzo Corporation and was added as indicated in aconcentration of about 1 to 250 parts per million by weight of thediluent. To prevent static buildup in the reactor, a small amount (<5ppm of diluent) of a commercial antistatic agent sold as Stadis® 450usually was added.

[0109] Ethylene was polymerization grade ethylene obtained from UnionCarbide Corporation. This ethylene was purified further through a columnof ¼ inch beads of Alcoa A201 alumina which had been activated at 250°C. in nitrogen. Isobutane was polymerization grade obtained fromPhillips Petroleum Co., Borger, Tex. It was purified further bydistillation and it too was passed through a column of ¼ inch beads ofAlcoa A201 alumina that had been activated at 250° C. in nitrogen. The1-hexene was polymerization grade obtained from Chevron Chemicals. Itwas purified further by nitrogen purging and storage over 13× molecularsieves that had been activated at 250° C.

[0110] Several bimodal polymers then were made in the continuous loopreactor by co-feeding two organometal compounds simultaneously. The samechlorided, zinc-containing alumina as described previously was used asthe activator, along with 250 ppm by weight of triisobutyl aluminum.Hexene was pumped into the reactor at the rate of 12.5 lbs per hour. Thehexene to ethylene feed weight ratio was 0.33. Reactor temperature was180° F. Density of the polymer was maintained at 0.920 g/cc, and thebulk density was about 22 lbs/cubic foot. The two organometal compoundsused were the inventive compound described previously, (CpTiCl₂)₂O,which produces the high molecular weight copolymer, andbis(n-butylcyclopentadienyl) zirconium dichloride also describedpreviously in Table 2, which produces the low molecular weight lessbranched polymer.

[0111] The relative amounts of the two organometal compounds were variedto produce five different polymers of varying breadth of molecularweight distribution. The GPC traces of the five polymers are shown inFIG. 1. Notice that as the inventive compound, (CpTiCl₂)₂O, is increasedin amount relative to the bis(n-butylcyclopentadienyl) zirconiumdichloride, the polymer molecular weight distribution broadens. Thepolydispersity (weight average molecular weight divided by numberaverage molecular weight) produced by the (CpTiCl₂)₂O alone was about 9,while the polydispersity of the bis(n-butylcyclopentadienyl) zirconiumdichloride alone was about 2.3. However, by combining the twoorganometal compounds, polydispersities of 12-17 was obtained,signifying greater breadth of molecular weight distribution.

[0112] While this invention has been described in detail for the purposeof illustration, it is not intended to be limited thereby but isintended to cover all changes and modifications within the spirit andscope thereof.

That which is claimed is:
 1. A process to produce a first catalystcomposition, said process comprising contacting at least one firstorganometal compound and at least one activator; wherein said firstorganometal compound is represented by the formula; R₂CpM¹—O—M²CpR₂wherein M¹ is selected from the group consisting of titanium, zirconium,and hafnium; wherein M² is selected from the group consisting of atransition metal, a lanthamide, an actinide, a Group IIIB metal, a GroupIVB metal, a Group VB metal, and a Group VIB metal; wherein Cp isindependently selected from the group consisting of cyclopentadienyls,indenyls, fluorenyls, substituted cyclopentadienyls, substitutedindenyls, and substituted fluorenyls; wherein substituents on saidsubstituted cyclopentadienyls, substituted indenyls, and substitutedfluorenyls of Cp are selected from the group consisting of aliphaticgroups, cyclic groups, combinations of aliphatic and cyclic groups,silyl groups, alkyl halide groups, halides, organometallic groups,phosphorus groups, nitrogen groups, silicon, phosphorus, boron,germanium, and hydrogen; wherein R is independently selected from thegroup consisting of halides, aliphatic groups, substituted aliphaticgroups, cyclic groups, substituted cyclic groups, combinations ofaliphatic groups and cyclic groups, combinations of substitutedaliphatic groups and cyclic groups, combinations of aliphatic groups andsubstituted cyclic groups, combinations of substituted aliphatic groupsand substituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted phosphido groups, alkyloxide groups,substituted alkyloxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, and substituted organometallic groups;and wherein said activator is selected from the group consisting ofaluminoxanes, fluoro-organic borate compounds, and treated solid oxidecomponents in combination with at least one organoaluminum compound. 2.A process according to claim 1 wherein said first organometal compoundis represented by the formula: (C₅R₅)TiX₂—O—(C₅R₅)TiX₂; wherein said Ris the same or different and is independently selected from the groupconsisting of hydrogen and a hydrocarbyl group having from 1 to about 10carbon atoms; wherein said hydrocarbyl group is selected from the groupconsisting of a linear or branched alkyl, a substituted or unsubstitutedaryl, and an alkylaryl; and wherein X is the same or different and isindependently selected from the group consisting of a halide, an alkyl,an alkylaryl having from 1 to about 10 carbon atoms, and a triflate. 3.A process according to claim 2 wherein said first organometal compoundis selected from the group consisting of [(C₅H₄CH₃)TiCl₂]₂O,[(C₅H₄CH₂C₆H₅)TiF₂]₂O, [(C₅H₃CH₃C₂H₅)TiBr₂]O, and [(C₅H₅)TiCl₂]₂O.
 4. Aprocess according to claim 3 wherein said first organometal compound is[(C₅H₅)TiCl₂]₂O.
 5. A process according to claim 1 wherein saidaluminoxanes are prepared from trimethylaluminum or triethylaluminum. 6.A process according to claim 5 wherein said aluminoxane is used incombination with a trialkylaluminum.
 7. A process according to claim 1wherein the molar ratio of the aluminum in said aluminoxane to thetransition metal in said first organometal compound is in a range ofabout 1:1 to about 100,000:1.
 8. A process according to claim 7 whereinthe molar ratio of the aluminum in said aluminoxane to the transitionmetal in said first organometal compound is in a range of 5:1 to15,000:1.
 9. A process according to claim 1 wherein said fluoro-organoborate compounds are selected from the group consisting ofN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)boron,N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, andmixtures thereof.
 10. A process according to claim 9 wherein the amountof said fluoro-organo borate compound is in a range of from about 0.5mole to about 10 moles of fluoro-organo borate compound per mole of saidfirst organometal compound.
 11. A process according to claim 10 whereinthe amount of said fluoro-organo borate compound is in a range of from0.8 mole to 5 moles of said fluoro-organo borate compound per mole ofsaid first organometal compound.
 12. A process according to claim 1wherein said treated solid oxide component is a halided solid oxidecomponent or a halided, metal-containing solid oxide component; whereinsaid halided solid oxide component comprises a halogen and a solid oxidecomponent; wherein said halided, metal-containing solid oxide componentcomprises a halogen, a metal, and a solid oxide component; wherein saidsolid oxide component is selected from the group consisting of alumina,silica-alumina, aluminophosphate, aluminoborate, and mixtures thereof;wherein said metal is selected from the group consisting of zinc,nickel, vanadium, copper, silver, gallium, tungsten, molybdenum, andtin; and wherein said halogen is chlorine or bromine.
 13. A processaccording to claim 12 wherein said organoaluminum compound is selectedfrom the group consisting of triisobutylaluminum, diethylaluminumhydride, dipentylalumium ethoxide, dipropylaluminum phenoxide, andmixtures thereof.
 14. A process according to claim 13 wherein saidorganoaluminum compound is triisobutylaluminum or triethylaluminum. 15.A process according to claim 12 wherein said solid oxide component has apore volume greater than about 0.8 cc/g.
 16. A process according toclaim 15 wherein said solid oxide component has a surface area in arange of about 200 to about 800 m²/g.
 17. A process according to claim16 wherein said solid oxide component is alumina.
 18. A processaccording to claim 17 wherein said halogen is chlorine.
 19. A processaccording to claim 18 wherein said metal is zinc.
 20. A process toproduce a first catalyst composition comprising contactingbis(cyclopentadienyl titanium dichloride) oxide, a chlorided,zinc-containing alumina, and an organoaluminum compound selected fromthe group consisting of triisobutyl aluminum and triethylaluminum toproduce said first catalyst composition; wherein the amount of zincpresent is in a range of about 0.5 millimoles to about 5 millimoles ofzinc per gram of alumina.
 21. A process according to claim 1 furthercomprising contacting a second organometal compound to produce a secondcatalyst composition; wherein said second organometal compound isrepresented by the formula (C₅R₅)₂ZrX₂; wherein said R is the same ordifferent and is independently selected from the group consisting ofhydrogen and a hydrocarbyl group having from 1 to about 10 carbon atoms;wherein said hydrocarbyl group is selected from the group consisting ofa linear or branched alkyl, a substituted or unsubstituted aryl, and analkylaryl; and wherein X can be the same or different and isindependently selected from the group consisting of a halide, an alkyl,an alkylaryl having from 1 to about 10 carbon atoms, and a triflate. 22.A process according to claim 21 wherein said second organometal compoundis bis(n-butylcyclopentadienyl)zirconium dichloride.
 23. A process toproduce a second catalyst composition, said process comprisingcontacting bis(cyclopentadienyl titanium dichloride)oxide,bis(n-butylcyclopentadienyl)zirconium dichloride, a chlorided,zinc-containing alumina, and triisobutyl aluminum.
 24. A catalystcomposition produced by the process of claim
 1. 25. A catalystcomposition produced by the process of claim
 21. 26. A catalystcomposition produced by the process of claim
 23. 27. A catalystcomposition according to claim 23 wherein said catalyst composition hasan activity greater than 1000 grams of polymer per gram of activator perhour under slurry polymerization conditions, using isobutane as adiluent, with a polymerization temperature of 90° C., and an ethylenepressure of 550 psig.
 28. A catalyst composition according to claim 27wherein said catalyst composition has an activity greater than 2000grams of polymer per gram of activator per hour under slurrypolymerization conditions, using isobutane as a diluent, with apolymerization temperature of 90° C., and an ethylene pressure of 550psig.
 29. A catalyst composition according to claim 23 wherein a weightratio of said organoaluminum compound to said treated solid oxidecomponent in said catalyst composition ranges from about 3:1 to about1:100.
 30. A catalyst composition according to claim 29 wherein saidweight ratio of said organoaluminum compound to said treated solid oxidecomponent in said catalyst composition ranges from 1:1 to 1:50.
 31. Acatalyst composition according to claim 23 wherein a weight ratio ofsaid treated solid oxide component to said organometal compound in saidcatalyst composition ranges from about 1000:1 to about 10:1.
 32. Acatalyst composition according to claim 31 wherein said weight ratio ofsaid treated solid oxide component to said organometal compound in saidcatalyst composition ranges from 250:1 to 20:1.
 33. A catalystcomposition according to claim 23 wherein said catalyst compositionsubsequent to contacting said organometal compound, said treated solidoxide component, and said organoaluminum compound consists essentiallyof organometal compound and said treated solid oxide component.
 34. Acatalyst composition according to claim 33 wherein said catalystcomposition subsequent to contacting said organometal compound, saidtreated solid oxide component, and said organoaluminum compound consistsessentially of organometal compound, said treated solid oxide component,and said organoaluminum compound.
 35. A catalyst composition accordingto claim 24 wherein said catalyst composition has an activity greaterthan 1000 grams of polymer per gram of activator per hour under slurrypolymerization conditions, using isobutane as a diluent, with apolymerization temperature of 90° C., and an ethylene pressure of 550psig.
 36. A catalyst composition according to claim 35 wherein saidcatalyst composition has an activity greater than 2000 grams of polymerper gram of activator per hour under slurry polymerization conditions,using isobutane as a diluent, with a polymerization temperature of 90°C., and an ethylene pressure of 550 psig.
 37. A catalyst compositionaccording to claim 24 wherein a weight ratio of said organoaluminumcompound to said treated solid oxide component in said catalystcomposition ranges from about 3:1 to about 1:100.
 38. A catalystcomposition according to claim 37 wherein said weight ratio of saidorganoaluminum compound to said treated solid oxide component in saidcatalyst composition ranges from 1:1 to 1:50.
 39. A catalyst compositionaccording to claim 23 wherein a weight ratio of said treated solid oxidecomponent to said first and second organometal compounds in saidcatalyst composition ranges from about 1000:1 to about 10:1.
 40. Acatalyst composition according to claim 39 wherein said weight ratio ofsaid treated solid oxide component to said first and second organometalcompounds in said catalyst composition ranges from 250:1 to 20:1.
 41. Apolymerization process comprising contacting at least one monomer andsaid catalyst composition of claim 23 under polymerization conditions toproduce a polymer.
 42. A process according to claim 41 wherein saidpolymerization conditions comprise slurry polymerization conditions. 43.A process according to claim 42 wherein said contacting is conducted ina loop reaction zone.
 44. A process according to claim 43 wherein saidcontacting is conducted in the presence of a diluent that comprises, inmajor part, isobutane.
 45. A process according to claim 41 wherein atleast one monomer is ethylene.
 46. A process according to claim 45wherein at least one monomer comprises ethylene and an aliphatic1-olefin having 3 to 20 carbon atoms per molecule.
 47. A polymerizationprocess comprising contacting at least one monomer and said catalystcomposition of claim 24 under polymerization conditions to produce abimodal polymer.
 48. A process according to claim 47 wherein saidpolymerization conditions comprise slurry polymerization conditions. 49.A process according to claim 48 wherein said contacting is conducted ina loop reaction zone.
 50. A process according to claim 49 wherein saidcontacting is conducted in the presence of a diluent that comprises, inmajor part, isobutane.
 51. A process according to claim 47 wherein atleast one monomer is ethylene.
 52. A process according to claim 51wherein at least one monomer comprises ethylene and an aliphatic1-olefin having 3 to 20 carbon atoms per molecule.
 53. A polymerproduced by the process of claim
 41. 54. A bimodal polymer produced bythe process of claim 47.